DE102004042933A1 - Solid formulated liquids for use in particulate detergents and cleaners - Google Patents

Abstract

In a process for the preparation of particulate detergents or cleaners, the incorporation of liquid components should be improved. Essentially, this is achieved by encapsulating liquid anhydrous detergent ingredient at room temperature in a fusible, water-soluble coating material solid at room temperature and admixing this encapsulation intermediate with the other solid and / or solid detergent or detergent ingredients.

Description

The The invention relates to granular detergents which are at room temperature liquid Active ingredient components in encapsulated form containing the corresponding encapsulated liquid Active ingredient components and a process for their preparation.

Detergents and cleaners usually contain a plurality of ingredients that contribute to the effectiveness of said agents and are therefore also referred to as active ingredient components. These include both those which directly and objectively relate to the washing or cleaning performance of the agent, such as surfactants, builders and enzymes, as well as those that satisfy more subjective aesthetic aspects, such as dyes and fragrances, but also those that the result of clean laundry to other positive effects, such as an improved grip or higher softness of treated with a detergent containing them. Some of these active ingredient components are solid, so that their incorporation into solid, in particular particulate detergents and cleaners poses no difficulties. However, some detergent ingredients are in liquid form at room temperature. These can be introduced in solid means only in amounts such that they can be absorbed by the other, in solid form quasi ingredients. If one adds more than the absorbency of the solids, which serve as a carrier material for the liquids corresponds to liquid ingredients, they swell out of the solid materials, stick the solid particles to larger, usually no longer flowable aggregates or even occur, especially in unfavorable camps - or packaging conditions, by the packaging material of the agent or go at least in this. Moreover, by no means all liquid washing or cleaning ingredients can be applied to any solid ingredients of such compositions and thus formulated in solid form; For example, consider only a H ₂ O ₂ -emitting particulate bleach which is to be charged with liquid bleach activator, or which, because the liquid lead activator runs out of a different type of particle, comes into contact with it. This would lead to the reaction of the two ingredients together so that they would no longer be available under the conditions of use of the agent and also could oxidatively affect other ingredients of the detergent or cleaning agent. Such reactive or sensitive liquid active ingredients are therefore usually formulated using inert carrier materials in solid form, which, however, usually have neither an objective nor subjective benefit in the application of the agent, but the actual active ingredient components only so to speak dilute, so that one strives is to keep their share in the finished detergent or cleaning agent as low as possible.

It has already been proposed to coat liquid-carrying solid particles in order to avoid the reaction between the liquid and other solid particles present in other particles. For example, from the European patent specification EP 0 684 984 B1 Compositions are known which contain mixtures of poorly water-soluble oil, which is located on an inorganic support material with a substance which is encapsulated in a water-sensitive matrix. The substance encapsulated in the water-sensitive matrix is a perfume, a flavor, a cosmetic active or an organometallic complex. Starch, maltodextrin, cyclodextrin, rubber, resins, polyvinylpyrrolidone, polyvinyl alcohol, cellulose esters and mixtures thereof are suitable as material for the water-sensitive matrix. The encapsulation in the water-sensitive matrix is carried out essentially for reasons of stability.

The German patent application DE 199 42 581 A1 relates to a process for the preparation of encapsulated liquid flavors and / or fragrances in which solid carrier material-containing aroma and / or fragrance particles are provided with a coating, wherein the coating contains a modified cellulose in which reversibly occurs gelation with temperature increase.

Granular detergents of high bulk density can be prepared according to the method of the European patent EP 0 486 592 getting produced. This is the strand-like compression of a homogeneous premix of Waschmitteunhaltsstoffen, which may optionally be carried out with the addition of a plasticizer, via hole shapes, which preferably have an opening width of 0.5 mm to 5 mm, then crushing of the extrudate by means of a cutting device and subsequent treatment in a Rondiergerät, which gives largely uniform spherical products. However, especially with surfactant-rich formulations, sometimes fissured surfaces of the extrudate grain and Length differences after knocking, which leads to a non-optimal increase in bulk density through the extrusion step, to increased fine and coarse parts and generally to a deterioration of the product image. In addition, if such surfactants are non-ionic surfactants which are relatively hydrophobic, in some instances inadequate solubility and reduced spargeability of the agent are observed. Also by other means, for example, by granulation process available detergents and cleaners can have the problems mentioned.

to Incorporation into solid, in particular particulate detergents and cleaners There is therefore a need for a solid composition which has such liquid Contains ingredients, when incorporated into liquid Form problems.

Surprisingly has now been found that at Room temperature liquid Ingredients of detergents or cleaning agents in particulate such Means can be incorporated if you take the liquid Ingredient in a water-soluble Material encapsulated. In order not to endanger the stability of the coating layer the wrapping material in the liquid Active substance not soluble his and the liquid Active substance may, because of the water solubility of the shell material, Accordingly, contain only so little water that the cladding even during storage does not rupture through the release process, respectively should be anhydrous. For reasons of manufacturability such liquid-filled capsules it is desirable if the wrapping material Although it is solid at room temperature, but at temperatures that at least short term with the liquid Active ingredient are compatible, liquid is present, so it can be melted.

One The first object of the invention is therefore a particle at room temperature liquid anhydrous detergent ingredient which is solid at room temperature fusible water-soluble wrapping material is encapsulated. The term "detergent ingredient" is intended here and hereinafter also include the term "detergent ingredient" if not explicitly is excluded. Such a particulate encapsulation product preferably has a content of liquid detergent ingredient in the range of 20% to 95% by weight, especially 25% to 85 wt .-% on. Under a liquid Fabric should be both a single component as well as a mixture several liquid Components that are immiscible or miscible with each other dissolved in each other could be, and also a solved one Solid particles contained liquid be understood. The consistency of the liquid detergent ingredient is not significant as long as it is pumpable as part of its processability is. Therefore, you can low-viscosity to high-viscosity, for example pasty, liquids be used.

Of the liquid Detergent ingredient is preferably nonionic surfactants, cationic surfactants, fragrances, silicone oils and mixtures of these selected.

Of the liquid Detergent ingredient may, if desired also in this unresolved present at room temperature solid detergent ingredient. The content of solid detergent ingredient, based on capsule-shaped particle, is preferably up to 50% by weight, in particular 1% by weight to 25% by weight. The encapsulation product preferably has a content of coating material in the range of 5 wt .-% to 30 wt .-%, in particular 7.5 wt .-% bis 25 wt .-%, with this amount of information that in the shell layer include contained material. If identical with wrapping material also in addition unresolved in the liquid Detergent ingredient that is inside the capsule, these amounts become those of the solid detergent ingredient. The one in question here upcoming solid detergent ingredient may be from the below standing solid detergent ingredients are selected and preferably includes at least partially inorganic materials. In addition, can the material to be encapsulated, that is the sum of liquid and - optionally missing - firm Detergent ingredient small amounts, preferably not more as 5 wt .-%, in particular 0.05 wt .-% to 3 wt .-% free water contain; preferably it is anhydrous, that is to say it is no water added and it does not have more water than through the processing for the particle according to the invention, for example from the air. The particle according to the invention preferably has an average particle diameter in the range from 0.5 mm to 2 mm, in particular 1.2 mm to 1.6 mm.

Such an encapsulation product is preferably prepared by heating the fusible, water-soluble coating material solid at room temperature above its melting point, introducing the anhydrous detergent ingredient liquid at room temperature and, optionally, the detergent ingredient solid at room temperature, and dropping it, and then dropping the drop under the steam cooling point of the wrapping material. In a preferred embodiment of the method, double droplets are used for dripping or for introducing and dripping, with the aid of which double droplets are produced, the detergent constituent or the detergent constituents being present in the inner droplet and the wrapping material in the outer droplet. Preferably, the dripping step is carried out under low pressure of the system to be dripped by means of vibrating nozzles. As a result, the rays emerging from the nozzle are constricted into individual segments and divided into uniform drops. The surface tension gives this droplet spherical shape, which is maintained by cooling below the solidification point of the wrapping material. The cooling can be achieved in a simple manner by the gas present in the falling section of the spherical drop, in particular air, which is heated to below the solidification point of the wrapping material. The most uniformity of the droplets results in a monomodal size distribution of the resulting capsules. Particular preference is given to using the microcapsule method, as it is available, for example, from BRACE GmbH. A uniform droplet formation when dripping can be achieved with a JetCutter (available from geniaLab ^® Biotechnology Products and Services GmbH) take place or be relieved. In this case, the falling liquid flow is divided by a rotating cutting tool into cylindrical segments, which also reach spherical shape by the surface tension.

One Another object of the invention is a process for the preparation of particulate Detergents or cleaning agents with increased content at room temperature liquid Ingredient, wherein at room temperature liquid anhydrous detergent ingredient in fusible, water-soluble solid at room temperature wrapping material encapsulated and this encapsulation intermediate the one or the other solid and / or detergent ingredients formulated in solid form admixed. In the method according to the invention for the production of detergents and cleaning agents are in the resulting washing or cleaning agent preferably 1 wt .-% to 50 wt .-%, in particular From 3% to 20% by weight of the particulate encapsulant product contain. In a preferred embodiment of the invention in the detergent or cleaning several different composite particulate encapsulation products incorporated, for example, a surfactant-filled capsule next to a perfume oil-filled capsule, a bleach activator filled Capsule, a capsule containing bleach-containing filling and / or a capsule with enzyme-containing filling.

conditioned through the very high uniformity the encapsulation products according to the invention In the use of these containing agents are the encapsulated liquids and optionally the solids contained in them normally released within a very short time interval since the cladding layer all virtually identical Capsules dissolves almost immediately. By choosing the type of wrapping material and / or by its layer thickness but can also - in accordance different types and / or layer thicknesses - a uniform release of the detergent ingredient over a longer one Period up to the entire period of application of the agent achieved be, if appropriately different encapsulated particles in the means are included. By the same measure, if desired, but also one targeted temporal order of release different Detergent ingredients, for example bleaches and / or bleach activator after enzyme, softening agent after bleach and / or bleach activator, and / or perfume after release all other detergent ingredients, if the previously released Active ingredient in a rapidly disintegrating capsule and / or a rapidly dissolving one other particulate Component of the agent is included.

When wrapping material are commercially available water-soluble Materials, especially polymers, solid at room temperature are, when heated to a temperature preferably in the range not exceeding 100 ° C, in particular 30 ° C to Melt 60 ° C and on cooling to freeze again.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der a1) Polyvinylpyrrolidone, a2) Vinylpyrrolidon/Vinylester-Copolymere;
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der b1) Alkylacrylamid/Acrylsäure-Copolymere b2) Alkylacrylamid/Methacrylsäure-Copolymere b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren und b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren;
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c3) Methacroylethylbetain/Methacrylat-Copolymere;
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der d1) Vinylacetat/Crotonsäure-Copolymere d2) Vinylpyrrolidon/Vinylacrylat-Copolymere d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen d5) gepfropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindestens einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestern d8iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen gegebenenfalls verzweigten Monocarbonsäure;
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der e1) quaternierten Cellulose-Derivate e2) Polysiloxane mit quaternären Gruppen e3) kationischen Guar-Derivate e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere e7) quaternierter Polyvinylalkohol e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Preferred water-soluble coating materials are selected from those listed below:

• a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers;
• b) water-soluble amphoteric polymers from the group of b1) alkylacrylamide / acrylic acid copolymers b2) alkylacrylamide / methacrylic acid copolymers b3) alkylacrylamide / methylmethacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids and b8iii) optionally further ionic or nonionic monomers;
• c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers;
• d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or im Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one nonionic type monomer, d5ii) at least one ionic type monomer, d5iii) from polyethylene glycol and d5iv) a crosslinked d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long chain Carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of d8i ) Crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers selected from ethylene, vinylbenzene, vinylmethyl ether, acrylamide and their water-soluble Salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic optionally branched monocarboxylic acid;
• e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) Copolymers of vinylpyrrolidone with quaternized derivatives of the dialkylamino acrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers indicated under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Soluble in water According to the invention, such materials are those at room temperature in water to more than 2.5 wt .-% are soluble.

preferred wrapping materials preferably at least partially comprise a substance the group wax, (optionally acetalized) polyvinyl alcohol, Polyvinyl pyrrolidone, polyethylene oxide and (optionally modified) Gelatin.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten können."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

can contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have hydrolysis degrees of 98-99 and 87-89 mol%, respectively So production reasons still a residual content of acyl, in particular Acetyl groups. The polyvinyl alcohols are characterized by the manufacturers Indication of the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few highly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable biologically. The water solubility can be by post-treatment with aldehydes (acetalization), by Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. The coatings of polyvinyl alcohol are broad impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however allow water vapor to pass through.

in the Within the scope of the present invention, it is preferred that the polyvinyl alcohol a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 Mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%. In a preferred embodiment, this is at least a set wrapping material at least 20% by weight, particularly preferably at least 40% by weight, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%.

Preferably, the entire shell material used is at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70th to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. Polyvinyl alcohols of a certain molecular weight range are preferably used, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 . The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500. According to the invention, preferred detergents are water soluble or water dispersible packaging characterized in that the water-soluble or water-dispersible packaging material comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio of MG (50%) MW (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648, L734, Mowiflex LPTC KSE 221 as well as the ex Compounds of Texas polymer such as Vinex 2034.

Further optionally usable polyvinyl alcohols are shown in the following table:

Other suitable polyvinyl alcohols are optionally ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ^®, 78 , B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH -20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK). Also suitable are ERKOL ^® grades from Wacker.

Of the Water content of preferred in PVAL encapsulated liquids is less as 10% by weight, preferably less than 8% by weight, more preferably less than 6% by weight, and more preferably less than 4% by weight.

The Water of PVAL can be obtained by post-treatment with aldehydes (acetalization) or ketones (ketalization) changed become. Being particularly preferred and pronounced because of it good cold water solubility Polyvinyl alcohols have proven particularly advantageous in this case, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof acetalized or have been ketalized. As extremely beneficial to use are the reaction products of PVAL and starch.

Farther let yourself the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impermeable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide but pass water vapor.

Examples of suitable water PVAL films are those available under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, also referred to as PVP in short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercial PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powder or as aqueous solutions.

Polyethylene glycols, which are also referred to as polyethylene oxides or PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), mainly by Hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common.

The wrapping material is preferably from the polyethylene glycols, waxes, optionally modified Gelatins, polyvinyl alcohols and mixtures thereof.

Under nonionic surfactants contained in the encapsulation product according to the invention could be, In particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols and / or carboxylic acid amides, the alkyl groups having 8 to 22 C atoms, preferably 12 to 18 C atoms, own, understood. The average degree of alkoxylation of these compounds is included usually from 1 to 25, preferably 3 to 18 and more preferably 6 to 10. You can in a known manner by reaction with the corresponding alkylene oxides getting produced. Also, products obtained by alkoxylation of fatty acid alkyl esters with 1 to 4 carbon atoms in the ester part according to the method of international Patent application WO 90/13533 can be produced, come into question. Prefers are among the carboxylic acid amide derivatives the ethanolamide derivatives of alkanoic acids having 8 to 22 C atoms, preferably 12 to 16 carbon atoms. To the candidate alcohol alkoxylates belong the ethoxylates and / or propoxylates of linear or branched chain Alcohols having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. Particularly suitable are the derivatives of fatty alcohols, although also their branched-chain isomers for the preparation of usable Alkoxylates can be used. Uses are accordingly particularly the ethoxylates primary Alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals as well their mixtures. The use of corresponding alkoxylates of one or polyunsaturated fatty alcohols, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, Linolenyl alcohol, gadoleyl alcohol and eruca alcohol possible. To be encapsulated according to the invention Nonionic surfactants are liquid at temperatures not above Room temperature.

An encapsulation product may additionally or alternatively also contain cationic surfactants and among these in particular those with textile-softening softening action, for example a tetraalkylammonium salt, preferably halide, with 1 or 2 long-chain and 3 or 2 short-chain alkyl radicals. These are either liquid themselves or are dissolved or undissolved as solids together with liquid active ingredients. It preferably has, as a corresponding laundry-softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol. These are known substances that can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. From the German patent DE 43 08 794 moreover, a process for the preparation of solid ester quats is known in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994) and LShapiro in Cosm.Toil. 109, 77 (1994).

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder. Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (I), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R^ICO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Preferred ester quats are quaternized fatty acid triethanolamine ester salts which follow formula (I),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in sum for 0 or. Numbers from 1 to 12, q represents numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. Preferably, technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also elaidic acid-rich C _16/18 fatty acid cuts are used. To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil fatty acid (iodine value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R ^I CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven to be particularly advantageous.

in der R^ICO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R^ICO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

in the R ^I CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ^I CO, R ⁴ and R ^{5 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R^ICO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (III) should be mentioned as a further group of suitable esterquats.

in the R ^I CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

Regarding the selection of the preferred fatty acids and the optimal degree of esterification apply the for (I) by way of example also for the esterquats of the formulas (Π) and (III). Usually get the esterquats in the form of 50 to 90 weight percent alcoholic solutions in the trade, which can be encapsulated as described, wherein Ethanol, propanol and isopropanol are the usual alcoholic solvents are.

To the solid and / or in the form of ready-made detergent or cleaner components, with which the encapsulation product can be mixed and / or which can be dissolved and / or undissolved in the liquid detergent ingredient, ie inside the capsule, in addition to solid individual raw materials such as powdered polycarboxylate cobuilders, for example alkali citrate, solid inorganic builder materials; such as zeolite-A, zeolite-P, zeolite-X and crystalline sheet silicates, and other inorganic salts such as alkali metal carbonate, alkali metal bicarbonate and alkali metal silicate, oxygen-based solid bleaching agents, for example alkali metal perborates, which may be present as so-called monohydrates or tetrahydrates, or alkali metal percarbons, also in powder form Bleach activators, for example one according to the method of the European patent EP 0 037 026 tetraacetylethylenediamine granules prepared, solid-form, high-active-substance anionic surfactant compounds, for example an alkyl sulphate compound prepared according to the process of international patent application WO 93/04162, enzymes in granular form, for example an enzyme extrudate prepared according to the process of international patent application WO 92/11347 or one according to the method of the German patent application DE 43 29 463 produced Mehrenzymgranulat and / or a powder, for example by the method of the German patent application DE 44 08 360 ready-to-use Soil release agent.

The Means can in addition to the surfactants mentioned or in their place, if appropriate other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in Quantities of preferably not over 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based to total agent, these being part of an inventively encapsulated liquid could be or otherwise, in particular as part of another particulate component, can be incorporated into the detergent or cleaning agent. When for the Use in such agents particularly suitable synthetic anionic surfactants are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms, the an alkali, ammonium or alkyl or hydroxyalkyl-substituted Wear ammonium ion as a counter cation to call. Preferred are the Derivatives of the fatty alcohols with in particular 12 to 18 C atoms and their branched-chain analogues, the so-called oxo alcohols. The Alkyl and alkenyl sulfates can in a known manner by reaction of the corresponding alcohol component with a usual Sulfation reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent Neutralization with alkali, ammonium or alkyl or Hydroxyalkyl-substituted ammonium bases are produced. To the sulfate-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Preferably included such ether sulfates 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the by reaction of fatty acid esters α-sulfoester obtainable with sulfur trioxide and subsequent neutralization, especially those of fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear Alcohols with 1 to 6 carbon atoms, preferably 1 to 4 C atoms, dissipative. sulfonation and the sulfo fatty acids resulting from formal saponification thereof.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight.

In a further embodiment contains the agent is water-soluble and / or water-insoluble builder, especially selected from Alkalialumosilikat, crystalline alkali metal silicate with modulus above 1, monomeric Polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% to 60% by weight.

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids , Maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably between 50,000 and 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred compounds of this class are copolymers of acrylic acid or Methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be for example a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides are preferred, particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in particular from 1% by weight to 35% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Amorphous alkali metal silicates are available, for example under the name Portil ^® commercially. Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si are used _x O _{2x + 1} · yH ₂ O in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular both β- and δ-sodium (Na ₂ Si ₂ O ₅ · yH ₂ O) are preferred, with β-sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171. δ-Sodium silicates with a Modulus between 1.9 and 3.2 can be made according to Japanese Patent Application JP 04/238809 or JP 04/260 610. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 452 428 can be used in agents which contain a polymer according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and / or the European patent application EP 0 294 753 are available are used in a further preferred embodiment of the invention means. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on water-free active substances, is then preferably 4: 1 to 10: 1.

In agents containing both amorphous and crystalline alkali silicates _; the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

An agent according to the invention may optionally contain bleaching agents, preferably peroxygen-based, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts ranging from 2% by weight to 10% by weight. , The bleaches which may be used are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali salts, in particular as sodium salts , present. Such bleaching agents are present in agents according to the invention preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, based in each case on the total agent especially percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. If they are not separated from them by an encapsulation according to the invention, the bleach activators may have been coated or granulated in known manner with encapsulating substances in order to avoid the interaction with the percompounds, granulated tetraacetylethylenediamine having average particle sizes of 0, with the aid of carboxymethylcellulose, 01 mm to 0.8 mm, as for example according to the European patent EP 37 026 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared by the process described in German Patent DD 255 884, and / or after the in Particularly preferred is the trialkylammonium acetonitrile prepared in particulate form in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

When Enzymes are especially those of the class of hydrolases, as the proteases, esterases, lipases or lipolytic acting Enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures the enzymes mentioned in question. All of these hydrolases carry in the Laundry for the removal of stains, such as protein, fat or starchy Stains, and graying at. Cellulases and other glycosyl hydrolases can by removing pilling and microfibrils for color maintenance and to increase contribute to the softness of the textile. To bleach respectively to inhibit color transfer can Oxidoreductases are also used.

Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and Li pase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.

enzymes can in usual Wise. particulate made up and / or encapsulated according to the invention in washing or Detergents are incorporated, taking in the case of encapsulation in admixture with said liquid detergent ingredients or optionally in an anhydrous solvent can. As a solvent, but at least they do not have to completely dissolve the enzyme, for example Polydiols, ethers, alcohols, ketones, amides and / or esters, in quantities from 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60 wt .-% to call. Preference is given to low molecular weight polar Substances such as methanol, ethanol, propylene carbonate, Acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, Ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide and mixtures thereof.

Of the Proportion of enzymes or enzyme mixtures, for example about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-% amount.

For the preparation of detergents or cleaners according to the invention, preference is given to a premix of from 20% by weight to 70% by weight of a builder- and surfactant-containing detergent product prepared by spray drying, from 3% by weight to 20% by weight of anionic surfactant compound according to WO 93/04162 containing more than 80% by weight, in particular more than 90% by weight, of alkyl sulfate having alkyl chain lengths in the range of C ₁₂ to C ₁₈ , the remainder being essentially inorganic salts and water, 2% to 10% by weight 5% by weight to 20% by weight of pulverulent, separately added polycarboxylate cobuilder, for example alkali citrate, 10% by weight to 20% by weight of peroxy bleach, for example sodium perborate monohydrate, and up to 20% by weight %, in particular 5 wt .-% to 20 wt .-% aqueous liquid components, for example water, aqueous alkali metal silicate and / or -polycarboxylatlösungen, produced and extruded, which after extrusion 1 wt .-% to 20 wt .-% of the invention according to the appropriate encapsulation product and, if desired, further solid or formulated in a solid form Waschbeziehungsweise detergent ingredients can be added.

The extrusion takes place under conditions known in principle, preferably using an extruder into which the homogeneous pre-mixture is fed and under a pressure in the range of preferably 30 bar to 180 bar, in particular 40 bar to 80 bar, through a perforated plate with a hole diameter of preferably 1.2 mm to 2.0 mm, in particular 1.4 mm to 1.7 mm extruded and shredded to a length which does not differ significantly from the thickness, that is, the hole diameter. Subsequently, the extrudate, optionally with the application of powdered solids as described in particular in the international patent application WO 94/01526, in a conventional Rondiergerät, for example a Spheronizer ^® , rounded and deburred. The encapsulated product admixed therewith deviates in its average diameter preferably as little as possible, in particular less than 10%, from the average diameter of the extruded constituent.

Claims (13)

Particles of liquid at room temperature anhydrous Detergent ingredient which is meltable at room temperature water-soluble wrapping material is encapsulated. Particles according to claim 1, characterized that the liquid at room temperature Detergent ingredient present in this unresolved, at room temperature contains solid detergent ingredient. Particles according to claim 1 or 2, characterized that the liquid Detergent ingredient of nonionic surfactants, cationic Surfactants, fragrances, silicone oils and mixtures selected from these becomes. Particles according to claim 2 or 3, characterized that the solid detergent ingredient is selected from inorganic materials. Particles according to one of Claims 1 to 4, characterized that it a content of from 20% to 95% by weight of liquid detergent ingredient, up to 50% by weight of solid detergent ingredient and 5% by weight to 30 wt .-% of wrapping material consists. Particles according to one of claims 1 to 5, characterized that this wrapping material from the polyethylene glycols, waxes, optionally modified Gelatinen, polyvinyl alcohols and mixtures thereof is selected. Particles according to one of Claims 1 to 6, characterized that the liquid Detergent ingredient, optional solid detergent ingredient and / or the capsule material contains dye. Particles according to one of Claims 1 to 7, characterized that it an average particle diameter in the range of 0.5 mm to 2 mm, in particular 1.2 mm to 1.6 mm. Process for the preparation of particles from at room temperature liquid anhydrous detergent ingredient which is solid at room temperature fusible water-soluble wrapping material is encapsulated by heating of wrapping material over his Melting point, introduction of the liquid Detergent ingredient and dripping and cooling of the Drop below the freezing point of the wrapping material. Method according to claim 9, characterized in that that he the introduction of the liquid Detergent ingredient and the dripping using a double nozzle makes. Method according to claim 9 or 10, characterized that he it performs as a microcapsule method. Method according to claim 9 or 10, characterized that he Do it with the help of a JetCutter. Process for the preparation of particulate washing or detergents with elevated Proportion of liquid at room temperature Ingredient characterized in that it is anhydrous at room temperature Detergent ingredient in fusible at room temperature water-soluble wrapping material encapsulated and this encapsulation intermediate the one or the other solid and / or detergent ingredients formulated in solid form admixed.